CN106732221B - A kind of preparation method of amphipathic Janus grading-hole micro-capsule having an open structure - Google Patents
A kind of preparation method of amphipathic Janus grading-hole micro-capsule having an open structure Download PDFInfo
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- CN106732221B CN106732221B CN201710043147.2A CN201710043147A CN106732221B CN 106732221 B CN106732221 B CN 106732221B CN 201710043147 A CN201710043147 A CN 201710043147A CN 106732221 B CN106732221 B CN 106732221B
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- Prior art keywords
- dehydrated alcohol
- microsphere
- capsule
- dispersed
- core shell
- Prior art date
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- 239000003094 microcapsule Substances 0.000 title claims abstract description 104
- 238000002360 preparation method Methods 0.000 title claims abstract description 61
- 239000004005 microsphere Substances 0.000 claims abstract description 144
- 239000000463 material Substances 0.000 claims abstract description 101
- 239000011258 core-shell material Substances 0.000 claims abstract description 70
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 52
- 238000000034 method Methods 0.000 claims abstract description 52
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 193
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 90
- 239000004793 Polystyrene Substances 0.000 claims description 71
- 229920002223 polystyrene Polymers 0.000 claims description 70
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 47
- 238000006243 chemical reaction Methods 0.000 claims description 43
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 42
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 42
- 235000019441 ethanol Nutrition 0.000 claims description 41
- 229960004756 ethanol Drugs 0.000 claims description 39
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 38
- 238000007306 functionalization reaction Methods 0.000 claims description 34
- 238000001291 vacuum drying Methods 0.000 claims description 34
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 claims description 30
- 238000005406 washing Methods 0.000 claims description 29
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 28
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 28
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 28
- 229910052681 coesite Inorganic materials 0.000 claims description 23
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- 239000011259 mixed solution Substances 0.000 claims description 22
- 235000019394 potassium persulphate Nutrition 0.000 claims description 22
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 21
- -1 amino, carboxyl Chemical group 0.000 claims description 19
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 18
- 239000006185 dispersion Substances 0.000 claims description 16
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 16
- 229960002380 dibutyl phthalate Drugs 0.000 claims description 15
- 239000000377 silicon dioxide Substances 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 15
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 13
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 12
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 9
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 8
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- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 6
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- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 5
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- 235000011152 sodium sulphate Nutrition 0.000 claims description 5
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 claims description 4
- 206010013786 Dry skin Diseases 0.000 claims description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
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- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 3
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- NXQYMTQFPYUABQ-UHFFFAOYSA-N carboxy(ethyl)silicon Chemical compound CC[Si]C(O)=O NXQYMTQFPYUABQ-UHFFFAOYSA-N 0.000 claims description 3
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- JYYOBHFYCIDXHH-UHFFFAOYSA-N carbonic acid;hydrate Chemical compound O.OC(O)=O JYYOBHFYCIDXHH-UHFFFAOYSA-N 0.000 claims description 2
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- YGUFXEJWPRRAEK-UHFFFAOYSA-N dodecyl(triethoxy)silane Chemical compound CCCCCCCCCCCC[Si](OCC)(OCC)OCC YGUFXEJWPRRAEK-UHFFFAOYSA-N 0.000 claims description 2
- SCPWMSBAGXEGPW-UHFFFAOYSA-N dodecyl(trimethoxy)silane Chemical compound CCCCCCCCCCCC[Si](OC)(OC)OC SCPWMSBAGXEGPW-UHFFFAOYSA-N 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- CZWLNMOIEMTDJY-UHFFFAOYSA-N hexyl(trimethoxy)silane Chemical compound CCCCCC[Si](OC)(OC)OC CZWLNMOIEMTDJY-UHFFFAOYSA-N 0.000 claims description 2
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- INJVFBCDVXYHGQ-UHFFFAOYSA-N n'-(3-triethoxysilylpropyl)ethane-1,2-diamine Chemical compound CCO[Si](OCC)(OCC)CCCNCCN INJVFBCDVXYHGQ-UHFFFAOYSA-N 0.000 claims description 2
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- SLYCYWCVSGPDFR-UHFFFAOYSA-N octadecyltrimethoxysilane Chemical compound CCCCCCCCCCCCCCCCCC[Si](OC)(OC)OC SLYCYWCVSGPDFR-UHFFFAOYSA-N 0.000 claims description 2
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
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- RKYSDIOEHLMYRS-UHFFFAOYSA-N triethoxy(hex-5-enyl)silane Chemical compound CCO[Si](OCC)(OCC)CCCCC=C RKYSDIOEHLMYRS-UHFFFAOYSA-N 0.000 claims description 2
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- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 claims 2
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- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 claims 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims 1
- 229910021529 ammonia Inorganic materials 0.000 claims 1
- XGZGKDQVCBHSGI-UHFFFAOYSA-N butyl(triethoxy)silane Chemical compound CCCC[Si](OCC)(OCC)OCC XGZGKDQVCBHSGI-UHFFFAOYSA-N 0.000 claims 1
- 239000002131 composite material Substances 0.000 claims 1
- CWAFVXWRGIEBPL-UHFFFAOYSA-N ethoxysilane Chemical compound CCO[SiH3] CWAFVXWRGIEBPL-UHFFFAOYSA-N 0.000 claims 1
- 238000002347 injection Methods 0.000 claims 1
- 239000007924 injection Substances 0.000 claims 1
- ARYZCSRUUPFYMY-UHFFFAOYSA-N methoxysilane Chemical compound CO[SiH3] ARYZCSRUUPFYMY-UHFFFAOYSA-N 0.000 claims 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N phthalic anhydride Chemical compound C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 claims 1
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- 239000002077 nanosphere Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
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- 230000005540 biological transmission Effects 0.000 description 2
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- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
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- KOUONPVXNPOEHQ-UHFFFAOYSA-N 2-[dimethoxy(propyl)silyl]oxyacetamide Chemical compound CCC[Si](OC)(OC)OCC(N)=O KOUONPVXNPOEHQ-UHFFFAOYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
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- HGWOWDFNMKCVLG-UHFFFAOYSA-N [O--].[O--].[Ti+4].[Ti+4] Chemical compound [O--].[O--].[Ti+4].[Ti+4] HGWOWDFNMKCVLG-UHFFFAOYSA-N 0.000 description 1
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- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
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Classifications
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
- B01J13/06—Making microcapsules or microballoons by phase separation
- B01J13/12—Making microcapsules or microballoons by phase separation removing solvent from the wall-forming material solution
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
- B01J13/06—Making microcapsules or microballoons by phase separation
- B01J13/14—Polymerisation; cross-linking
- B01J13/18—In situ polymerisation with all reactants being present in the same phase
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F112/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F112/02—Monomers containing only one unsaturated aliphatic radical
- C08F112/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F112/06—Hydrocarbons
- C08F112/08—Styrene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/12—Powdering or granulating
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2325/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
- C08J2325/02—Homopolymers or copolymers of hydrocarbons
- C08J2325/04—Homopolymers or copolymers of styrene
- C08J2325/06—Polystyrene
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Abstract
The present invention is a kind of preparation method of amphipathic Janus grading-hole micro-capsule having an open structure.This method is modified by first carrying out occupy-place to the outer surface of core shell complex microsphere, then core shell microballoon be first swollen being formed after the anisotropic complex microsphere with protrusion and remove removing template with good solvent dissolution again to form the micro-capsule of hatch frame, different function finally is carried out to micro-capsule inner surface, obtains that inner surface hydrophilic outer surface is hydrophobic or the microencapsulated material of hydrophobic inner surface and hydrophilic outer surface.The material that the present invention obtains has excellent biocompatibility, good organic solvent resistance, resistance to chemical corrosion and high mechanical stability, has huge potential using value in fields such as micro-nano reactor, supported catalysts.
Description
Technical field
Technical solution of the present invention is related to organic and inorganic and polymeric material field, and in particular to one kind has opening
The preparation method of the amphipathic Janus grading-hole micro-capsule of structure.
Background technique
In recent years, there is the micro-capsule of porous structure since it is with low density, high specific surface area, good on shell
The competitive advantages such as permeance property, sufficiently exposed surfaces externally and internally can be widely applied to catalysis (Jiafu Shi, et
al.Incorporating Mobile Nanospheres in the Lumen of Hybrid Microcapsules for
Enhanced Enzymatic Activity[J].ACS Applied Materials&Interfaces,2013,5,10433-
10436.), micro-nano reactor (Fuping Dong, et al.Controlled synthesis of novel
cyanopropyl polysilsesquioxane hollow spheres loaded with highly dispersed Au
nanoparticles for catalytic applications[J].Chemical Communications,2012,48,
1108-1110), drug controlled release (Yingjie Wu, et al.Self-Propelled Polymer Multilayer
Janus Capsules for Effective Drug Delivery and Light-Triggered Release[J].ACS
Applied Materials&Interfaces, 2014,6 (13), 10476-10481), adsorption-desorption (Yingmei Liu, et
al.A Novel Smart Microsphere with Magnetic Core and Ion-Recognizable Shell
for Pb2+Adsorption and Separation[J].ACS Applied materials&Interfaces,2014,6
(12), 9530-9542.) etc. fields.The type of micro-capsule includes organic and inorganic and hybridized microcapsule etc..Wherein, inorganic micro-capsule by
It gets more and more people's extensive concerning in the mechanical strength of its superelevation and good biocompatibility.In most cases, closed
Microcapsule structure, thick shell substantially increase the resistance to mass tranfer between micro-capsule blister cavities and system liquid.However, if by micro-capsule
Hatch frame on cyst wall is effectively combined the mass transfer rate that can significantly improve inside and outside cyst wall with mesoporous, greatlys improve and urges
Change efficiency (Jiafu Shi, Shaohua Zhang, et al.A Yolk-Shell Nanoreactor with a Basic
Core and an Acidic Shell for Cascade Reactions[J].Angewandte Chemie
International Edition,2014,50,12500-12503.).There is anisotropic Janus particle in chemical property
It is a kind of special colloidal materials, such as there is acidity/alkalinity (Yan Yang, Qihua Yang, et simultaneously
al.Selective Functionalization of Hollow Nanospheres with Acid and Base
Groups for Cascade Reactions[J].Chemistry A European Journal Communication,
2012,51,9164-9168.), hydrophilic/hydrophobic (Wei Cao, Renliang Huang, Wei Qi, et al.Self-
Assembly of Amphiphilic Janus Particles into Monolayer Capsules for Enhanced
Enzyme Catalysis in Organic Media[J].ACS Applied Materials&Interfaces,2015,7,
465-473.) etc..Janus material has widely potential answer in fields such as optical probe, assembling, catalysis and particle emulsifying agents
With, however the Janus micro-capsule for preparing selectively functionalized is still a challenge, especially carries out function to the inner surface of micro-capsule
Change.
This patent designs and is prepared for the complex microsphere based on organic/inorganic core-shell structure, modified using regioselectivity
It is first swollen the mode for going template to combine again and has prepared amphipathic Janus grading-hole micro-capsule (micro-capsule having an open structure
Material be related to SiO2、TiO2).This micro-capsule is by hatch frame (Open-mouthed), hierarchical porous structure, hollow structure, amphiphilic
Property is cleverly combined together, and the material is made to have huge potential using value.
Summary of the invention
The purpose of the present invention is provide a kind of having an open structure amphipathic for deficiency present in current techniques
The preparation method of Janus grading-hole micro-capsule.This method is modified by first carrying out occupy-place to the outer surface of core shell complex microsphere, so
Removing template is removed with good solvent dissolution again after carrying out anisotropic complex microsphere of the first swelling formation with protrusion to core shell microballoon afterwards
The micro-capsule of hatch frame is formed, different function finally is carried out to micro-capsule inner surface, to make it in micro-nano reactor, load
There is huge potential using value in the fields such as catalysis, have widened its application in catalytic field.
The technical scheme is that
A kind of preparation method of amphipathic Janus grading-hole micro-capsule having an open structure, method includes the following steps:
1) average particle size range is following two method in the preparation of the linear polystyrene template microsphere of 80~1000nm
One of:
Method one: polyvinylpyrrolidone is used to prepare linear polystyrene moulding microballoon as emulsifier
Water and polyvinylpyrrolidone (PVP) are added in the reactor, 10min is stirred, under protection of argon gas by styrene
Monomer is added in reaction system, emulsifies 30min, after system temperature is risen to 70 DEG C, potassium peroxydisulfate (KPS) solution is added dropwise to
In reaction system, after reacting 10~15h under stiring, stop reaction, by material centrifugal sedimentation, obtain 80 after vacuum drying~
Monodispersed linear polystyrene (LPS) template microsphere of 1000nm range；
It is water that its material proportion, which is volume ratio: styrene: KPS solution=90:10:10；In the water of 90mL be added 0.01~
The PVP of 9.0g；The concentration of KPS solution is in the water of 10mL dissolved with 0.01~0.8g potassium peroxydisulfate；
Alternatively, method two: dodecyl sodium sulfate being used to prepare linear polystyrene moulding microballoon as emulsifier
Water and sodium bicarbonate, dodecyl sodium sulfate (SDS) are added in the reactor, stirs 10min, under protection of argon gas
Styrene monomer is added in reaction system, 30min is emulsified, it is after system temperature is risen to 70 DEG C, potassium peroxydisulfate (KPS) is molten
Drop adds in reaction system, after reacting 10~15h under stiring, stops reaction, by material centrifugal sedimentation, after vacuum drying
To monodispersed linear polystyrene (LPS) template microsphere of 80~1000nm range；
It is water that its material proportion, which is volume ratio: styrene: KPS solution=12:2:3；In the water of 240mL be added 0.025~
The sodium bicarbonate of the SDS and 0.05~0.4g of 2g；The concentration of KPS solution is in the water of 60mL dissolved with 0.1~0.9g potassium peroxydisulfate；
2) preparation of core shell complex microsphere is one of following four method:
One: PVP method of method prepares LPS SiO2Core shell complex microsphere
The linear polystyrene template microsphere of PVP functionalization obtained in dry step 1) method one is dispersed in anhydrous
In ethyl alcohol, ammonium hydroxide and water are successively added into system, after stirring 5~20min, ethyl orthosilicate (TEOS) is added into system,
After reacting 6~10h at room temperature, by resulting material ethanol washing, carries out vacuum drying and obtain LPS@SiO2Core shell is compound
Microballoon；
It is dehydrated alcohol that its material proportion, which is volume ratio: ammonium hydroxide: water: TEOS=120:0.1~1.2:1~16:1~16；
Every 0.1g linear polystyrene template microsphere is dispersed in the dehydrated alcohol of 5~20mL；
Alternatively, method two: sulfonation method prepares LPS@SiO2Core shell complex microsphere
Linear polystyrene template microsphere obtained in dry step 1) method two is impregnated in concentrated sulfuric acid at room temperature
Then 10~30min reacts 0.25~8h at 40 DEG C of dislocation, material is washed till neutrality with water after reaction, after freeze-drying
Obtain the polystyrene microsphere of sulfonic acid group functionalization；
The polystyrene microsphere of dry sulfonic acid group functionalization is dispersed in dehydrated alcohol, is successively added into system
TEOS, water, react 10 at room temperature~for 24 hours, two are washed to obtaining LPS@SiO three times, after vacuum drying with ethyl alcohol after reaction2
Core shell complex microsphere；
Its material proportion is that the amount of the corresponding concentrated sulfuric acid of every sulfonation 1g linear polystyrene template microsphere is 20~80mL；Often
The polystyrene microsphere of 1g sulfonic acid group functionalization is dispersed in the dehydrated alcohol of 50~200mL；Volume ratio is dehydrated alcohol:
TEOS: water=10:0.2~2:0.2~2；
Alternatively, three: PVP method of method prepares LPS TiO2Core shell complex microsphere
The linear polystyrene template microsphere of PVP functionalization obtained in dry step 1) method one is dispersed in anhydrous
In ethyl alcohol, by Butyl Phthalate (TBT)/dehydrated alcohol mixed solution note into above-mentioned dispersion liquid, 6~12h is stirred at room temperature,
Unadsorbed TBT is washed away with dehydrated alcohol, and then obtained material is dispersed in dehydrated alcohol, water is added into system,
6~12h is reacted at room temperature, is arrived with ethanol washing two obtain LPS@TiO three times, after vacuum drying after reaction2Core shell is compound
Microballoon；
Its material proportion is that the linear polystyrene template microsphere of every 1g PVP functionalization is dispersed in the anhydrous of 25~100mL
In ethyl alcohol, and into dispersion liquid inject 20~80mL TBT/ dehydrated alcohol mixed solution；In mixed solution, volume ratio without
Water-ethanol: TBT=1:0.5~2；Every 1g washes away the material after unadsorbed TBT and is dispersed in the dehydrated alcohol of 25~100mL,
Volume ratio is dehydrated alcohol needed for dispersion washes away the material after unadsorbed TBT: water=1:0.5~2；
Alternatively, method four: sulfonation method prepares LPS@TiO2Core shell complex microsphere
Linear polystyrene template microsphere obtained in dry step 1) method two is impregnated in concentrated sulfuric acid at room temperature
Then 10~30min reacts 0.25~8h at 40 DEG C of dislocation, material is washed till neutrality with water after reaction, after freeze-drying
Obtain the polystyrene microsphere of sulfonic acid group functionalization；
The polystyrene microsphere of the sulfonic acid group functionalization of these dryings is dispersed in dehydrated alcohol, by Butyl Phthalate
(TBT)/dehydrated alcohol mixed solution is infused into above-mentioned dispersion liquid, and 6~12h is stirred at room temperature, is washed away not with dehydrated alcohol
Then obtained material is dispersed in dehydrated alcohol by the TBT of absorption, water is added into system, reacts 6~12h at room temperature,
Two are washed to obtaining LPS@TiO three times, after vacuum drying with ethyl alcohol after reaction2Core shell complex microsphere；
Its material proportion is that the amount of the corresponding concentrated sulfuric acid of every sulfonation 1g linear polystyrene template microsphere is 20~80mL；Often
The polystyrene microsphere of 1g sulfonic acid group functionalization is dispersed in the dehydrated alcohol of 25~100mL, and is injected into dispersion liquid
The mixed solution of the TBT/ dehydrated alcohol of 20~80mL；In mixed solution, volume ratio is dehydrated alcohol: TBT=1:0.5~2；Often
1g washes away the material after unadsorbed TBT and is dispersed in the dehydrated alcohol of 25~100mL；Volume ratio washes away unadsorbed for dispersion
Dehydrated alcohol needed for after the microballoon of TBT: water=1:0.5~2；
3) preparation of hydrophobic, the hydrophilic core shell complex microsphere in outer surface
Method one: the preparation of the hydrophobic core shell complex microsphere in outer surface
Any one in four kinds of core shell complex microspheres obtained in dry step 2) is dispersed in dehydrated alcohol,
The silane coupling agent being added into system after reacting 5~12h at 80 DEG C, by resulting material ethanol washing, carries out vacuum
It is dry to obtain the hydrophobic core shell complex microsphere in outer surface；
Its material proportion is dispersed in the dehydrated alcohol of 5~20mL for every 0.1g core shell complex microsphere, and addition 20~
120 μ L silane coupling agents；Silane coupling agent is the silane coupling agent with hydrophobic chain；
Method two: the preparation of the core shell complex microsphere of surface and hydrophilic outer
Any one in four kinds of core shell complex microspheres obtained in dry step 2) is dispersed in dehydrated alcohol,
Silane coupling agent is added into system, after reacting 5~12h at 80 DEG C, by resulting material ethanol washing, it is dry to carry out vacuum
The dry core shell complex microsphere for obtaining surface and hydrophilic outer；
Its material proportion are as follows: every 0.1g core shell complex microsphere is dispersed in the dehydrated alcohol of 5~20mL, and is added 20
~120 μ L silane coupling agents；Silane coupling agent be end with amino, carboxyl, sulfydryl silane coupling agent；
4) preparation of grading-hole micro-capsule having an open structure
By the core shell of the hydrophobic core shell complex microsphere in outer surface obtained in dry step 3) or surface and hydrophilic outer
Complex microsphere is dispersed in dehydrated alcohol, and tetrahydrofuran (THF)/dehydrated alcohol mixed solution is injected into rapidly reaction system
In, it is swollen 0.2~2h at room temperature, obtains anisotropic complex microsphere, then material is centrifuged out with pure THF centrifugation
Washing 3~5 times, then THF is washed with ethyl alcohol, it is hydrophobic or outer to can be prepared by outer surface having an open structure after vacuum drying
The grading-hole micro-capsule of surface hydrophilic；
The core shell complex microsphere of the hydrophobic core shell complex microsphere in every outer surface 0.2g or surface and hydrophilic outer is dispersed in 1~
In the dehydrated alcohol of 8mL, and into dispersion liquid inject 2~16mL THF/ dehydrated alcohol mixed solution；In mixed solution,
Volume ratio is THF: dehydrated alcohol=1~6:6；
5) micro-capsule inner surface carries out hydrophobic, hydrophile function
Method one: the preparation of the hydrophobic Janus grading-hole micro-capsule of inner surface hydrophilic outer surface
The hydrophobic grading-hole micro-capsule in obtained outer surface having an open structure is dispersed in dehydrated alcohol, into system
Silane coupling agent is added, after reacting 5~12h at 80 DEG C, by resulting material ethanol washing, carries out vacuum drying and acquires
The hydrophobic Janus grading-hole microencapsulated material of inner surface hydrophilic outer surface；
Its material proportion are as follows: every 0.05g grading-hole micro-capsule is dispersed in 5~40mL dehydrated alcohol, and is added 20~240
μ L silane coupling agent；Silane coupling agent be end with amido, carboxyl, sulfydryl silane coupling agent；
Method two: the preparation of the Janus grading-hole micro-capsule of hydrophobic inner surface and hydrophilic outer surface
The grading-hole micro-capsule of obtained surface and hydrophilic outer having an open structure is dispersed in dehydrated alcohol, into system
Silane coupling agent is added, after reacting 5~12h at 80 DEG C, by resulting material ethanol washing, carries out vacuum drying and acquires
The Janus grading-hole microencapsulated material of hydrophobic inner surface and hydrophilic outer surface；
Its material proportion are as follows: every 0.05g grading-hole micro-capsule is dispersed in 5~40mL dehydrated alcohol, and is added 20~240
μ L silane coupling agent；Silane coupling agent is the silane coupling agent with hydrophobic chain.
Silane coupling agent of the end with carboxyl is specially three sodium alkoxide of carboxyethylsilane.
Silane coupling agent of the end with sulfydryl is 3- mercaptopropyl trimethoxysilane, 3- mercapto propyl-triethoxysilicane
Alkane or 11- mercapto-undecanoic base trimethoxy silane.
Silane coupling agent of the end with amido is 3- aminopropyl triethoxysilane, 3- aminopropyl trimethoxy silicon
Alkane, 4- ammobutyltriethoxysilane, N- (2- amino-ethyl)-aminopropyl triethoxysilane, N- (2- amino-ethyl)-ammonia
Propyl trimethoxy silicane, N- (6- Aminohexyl) amino methyl triethoxysilane, N- [3- trimethoxy first silicon substrate] third
Base] -1,6- hexamethylene diamine, 11- amino-undecanoic ethyl triethoxy silicane alkane, 3- (4- Semicarbazido) propyl-triethoxysilicane or diethyl
Three aminocarbonyl propyl trimethoxy silane of alkene.
Silane coupling agent of the end with hydrophobic chain is octadecyl trimethoxysilane, octadecyl triethoxy
Silane, hexadecyl trimethoxy silane, hexadecyl, dodecyltrimethoxysilane, dodecyl
Triethoxysilane, eight alkyl trimethoxysilanes, eight alkyl triethoxysilanes, n-hexyl trimethoxy silane, n-hexyl
Triethoxysilane, trimethoxy-(2,4,4- tri-methyl-amyl) silane, triethoxy-(2,4,4- tri-methyl-amyl) silane,
Vinyltriethoxysilane, 5- hexenyl triethoxysilane, 7- octenyl trimethoxy silane, 10- alkenyl undecyl
Trimethoxy silane.1H, 1H, 2H, 2H- perfluoro capryl triethoxysilane, 1H, 1H, 2H, 2H- perfluoro capryl trimethoxy silicon
Alkane, trimethoxy (nine fluorine hexyl of 1H, 1H, 2H, 2H-) silane or triethoxy (nine fluorine hexyl of 1H, 1H, 2H, 2H-) silane.
The beneficial effects of the present invention are:
(1) present invention utilizes PVP or the carbonyl or sulphur on the linear polystyrene template microsphere surface of sulfonic acid group functionalization
Acidic group, carbonyl, which can form strong hydrogen bond with the hydroxyl of silica or TiO 2 precursor, makes silica or titanium dioxide
Titanium is deposited on Surfaces of Polystyrene Microparticles and carries out growth or sulfonic acid group inducing catalysis silica or titanium dioxide progress original
Position growth after core shell complex microsphere is made, using regioselectivity occupy-place modification and carries out first being swollen the side for dissolving template afterwards
Method, can be prepared by amphipathic Janus grading-hole micro-capsule having an open structure, and the performance of material, structure and preparation thinking are new
It is had not been reported in clever document, preparation is simple, it is easy to accomplish scale, industrialization production have preferable industry hair
Exhibition prospect.
(2) one kind prepared by the present invention amphipathic Janus grading-hole micro-capsule having an open structure, it is multiple in obtained core shell
After closing microballoon, without carrying out complicated hole forming technology, the grading-hole formed by the mesoporous and macropore rank on cyst wall can be prepared by
The micro-capsule of structure amphipathic is incorporated into hatch frame, hierarchical porous structure, hollow structure and cleverly one.From attached drawing
Electromicroscopic photograph to can be seen that shell accumulated by the nano particle of silica, the gap of accumulation forms mesoporous knot
Structure, and remove after polystyrene moulding on the cyst wall of micro-capsule with uniform hatch frame, hierarchical porous structure can make object
Matter enters from all directions, forms multiphase mass transfer.Micro-capsule has very thin cyst wall, advantageously reduces the mass transfer of matrix and product
Resistance greatly promotes mass transfer rate.
(3) one kind prepared by the present invention amphipathic Janus grading-hole micro-capsule having an open structure, by with different silane
The inner surface hydrophilic outer surface of coupling agent preparation is hydrophobic, micro-capsule of hydrophobic inner surface and hydrophilic outer surface its to be equivalent to bionic thin
Born of the same parents' structure.Microcapsule wall material is inorganic silicon dioxide, titanic oxide material, can adapt to separation demand, recycling performance
It is good.And the material has excellent biocompatibility, good organic solvent resistance, resistance to chemical corrosion and high
Mechanical stability has huge potential using value in fields such as micro-nano reactor, supported catalysts.
Detailed description of the invention
Fig. 1: the preparation flow figure of amphipathic Janus grading-hole micro-capsule having an open structure；
Fig. 2: the SEM photograph of linear polystyrene moulding microballoon in embodiment one；
Fig. 3: LPS@SiO in embodiment one2The SEM photograph of core shell complex microsphere；
Fig. 4: LPS@SiO in embodiment one2(LPS@SiO after hydrophobically modified2- HETMS) contact angle；
Fig. 5: anisotropic LPS@SiO in embodiment one2The SEM photograph of-HETMS complex microsphere；
Fig. 6: grading-hole SiO having an open structure in embodiment one2The SEM photograph of-HETMS micro-capsule；
Fig. 7: grading-hole SiO having an open structure in embodiment one2The STEM photo of-HETMS micro-capsule；
Fig. 8: amphipathic Janus grading-hole APTES-SiO having an open structure in embodiment one2- HETMS micro-capsule connects
Feeler；
Fig. 9: amphipathic Janus grading-hole APTES-SiO having an open structure in embodiment one2- HETMS micro-capsule it is interior
The TEM photo of area load gold particle；
Figure 10: amphipathic Janus grading-hole APTES-SiO having an open structure in embodiment two2- HETMS micro-capsule
Contact angle；
Figure 11: amphipathic Janus grading-hole APTES-SiO having an open structure in embodiment two2- HETMS micro-capsule
SEM photograph；
Specific embodiment
Preparation flow of the invention is as shown in Fig. 1, and (1) passes through the linear polyphenyl for preparing PVP or sulfonic acid group functionalization
Ethylene (LPS) template microsphere, and core shell complex microsphere is prepared by sol-gel process in polystyrene surface, (2) are used
Silane coupling agent carries out hydrophobic, hydrophilic modifying to the outer surface of core shell complex microsphere, and (3) are obtained anisotropic by swelling
Complex microsphere, (4) with good solvent remove LPS template obtain outer surface functionalization having an open structure Janus grading-hole it is micro-
Capsule, (5) carry out that hydrophobic, hydrophilic modifying, which prepares one kind, has with the inner surface of the external surface-functionalized micro-capsule of silane coupling agent
The amphipathic Janus grading-hole micro-capsule of hatch frame.
Preparation process flow of the present invention is simple, and reaction condition is mild, and products therefrom has preferable thermal stability and excellent
Different biocompatibility, and surfaces externally and internally, the efficient mass transfer rate, good Surface Permeability, high machine sufficiently exposed
Tool intensity makes it have huge potential using value in fields such as micro-nano reactor, supported catalysts.
Wherein, silane coupling agent of the end with carboxyl is specially three sodium alkoxide of carboxyethylsilane, is known material
Material is that the further acidification of carboxylic acid sodium salt process forms carboxylic acid.Lu Han, Shunai Che, et can also be referred to
al.Synthesis and Characterization of the Amphoteric Amino Acid Bifunctional
Mesoporous Silica[J].Chemistry of Materials,2007,19,2860-2867.
Silane coupling agent of the end with sulfydryl is 3- mercaptopropyl trimethoxysilane, 3- mercapto propyl-triethoxysilicane
Alkane or 11- mercapto-undecanoic base trimethoxy silane, are well known materials, and sulfydryl forms sulfonic acid group by further oxidation.?
Yan Yang, Qihua Yang, et al.Selective Functionalization of Hollow can be referred to
Nanospheres with Acid and Base Groups for Cascade Reactions[J].Chemistry A
European Journal Communication,2012,51,9164-9168.
Embodiment one:
(1) preparation of the linear polystyrene template microsphere of 800nm PVP functionalization
The water and 0.025g polyvinylpyrrolidone (PVP) for taking 90mL are added in the there-necked flask of 500mL, stir 10min,
It is passed through argon gas, by the monomer dropping of the styrene of 10mL into reaction system, emulsifies 30min, while system temperature is risen to 70
DEG C, it takes the potassium peroxydisulfate of 0.1g to be dissolved in the water of 10mL, potassium persulfate solution is added drop-wise in reaction system with 30min, stir
Speed control stops reaction after reacting 13h in 180r/min, obtains average grain diameter by material centrifugal sedimentation, after vacuum drying and is
The linear polystyrene template microsphere of 800nm；
Attached drawing 2 is with 450 scanning of scanning electron microscope linear polystyrene template microsphere of model FEI Nano SEM
Obtained SEM photograph, it can be seen from the figure that there is high list by linear polystyrene template microsphere prepared by emulsion polymerization
Dispersibility；
(2)LPS@SiO2The preparation of core shell complex microsphere
The linear polystyrene template microsphere of dry 2g PVP functionalization is dispersed in 120mL dehydrated alcohol, successively
540 μ L ammonium hydroxide (28Wt%) and 5mL water are added into system, after stirring 5min, 8mL ethyl orthosilicate is added into system,
At room temperature after (25 DEG C) reaction 10h, by resulting material ethanol washing, carries out vacuum drying and obtain LPS@SiO2Core shell is multiple
Close microballoon；
Attached drawing 3 is with 450 scanning of scanning electron microscope LPS@SiO of model FEI Nano SEM2Core shell is compound micro-
The SEM photograph that ball obtains, it can be seen from the figure that LPS@SiO2Core shell complex microsphere has uniform clad and surface
It is relatively rough, because shell is accumulated by nano SiO 2 particle, and SiO2The gap of nano particle accumulation forms shell
High efficiency of transmission mesoporous on layer, that mesoporous presence has conducive to substance；
(3) the LPS@SiO of outer surface hydrophobically modified2The preparation of complex microsphere
By dry 0.1g LPS@SiO2Core shell complex microsphere is dispersed in 10mL dehydrated alcohol, and 60 are added into system
After reacting 10h at 80 DEG C, resulting material ethanol washing carries out true for μ L hexadecyl trimethoxy silane (HETMS)
Sky is dry to obtain the hydrophobic LPS@SiO in outer surface2Complex microsphere (LPS@SiO2-HETMS)；
Attached drawing 4 is to useThe PS@SiO that model DSA30 optical contact angle measuring instrument measures2Complex microsphere is hydrophobic to be changed
Property after contact angle (157.8 °), it was demonstrated that hydrophobically modified success；
(4) grading-hole SiO having an open structure2The preparation of-HETMS micro-capsule
By the hydrophobic 0.2gLPS SiO in outer surface obtained in dry step (3)2- HETMS complex microsphere is dispersed in
In 4mL dehydrated alcohol, 8mL tetrahydrofuran (THF)/dehydrated alcohol (1:1v/v) mixed solution is injected into rapidly reaction system
In, (25 DEG C) swelling 1h, obtain anisotropic LPS@SiO at room temperature2Material, is then centrifuged out by-HETMS complex microsphere
To use pure THF centrifuge washing 3-5 times, then with ethyl alcohol THF is washed, can be prepared by after vacuum drying having an open structure outer
The grading-hole SiO of surface hydrophobicity2- HETMS micro-capsule；
Attached drawing 5 is with the anisotropic LPS@SiO of 450 scanning of scanning electron microscope of model FEI Nano SEM2It is multiple
The SEM photograph that microballoon obtains is closed, it can be seen from the figure that anisotropic complex microsphere consists of two parts, smooth part is
Linear polystyrene, coarse part are silica shells, and protrusion is generated after swelling and is conducive to form hatch frame on cyst wall；
Attached drawing 6 is to remove linear polystyrene template with 450 scanning of scanning electron microscope of model FEI Nano SEM
The grading-hole SiO having an open structure obtained afterwards2The SEM photograph of-HETMS micro-capsule, as can be seen that micro-capsule is kept from photo
Complete pattern, have both mesoporous and macroporous structure on cyst wall；
Attached drawing 7 is the removal linear polystyrene mould with 450 scanning of scanning electron microscope of model FEI Nano SEM
The grading-hole SiO having an open structure obtained after plate2The STEM photo of-HETMS micro-capsule can be seen that micro-capsule from photo
Hatch frame on hollow structure and cyst wall；
(5) to SiO2- HETMS micro-capsule inner surface carries out hydrophile function
By the hydrophobic SiO in outer surface obtained in dry 0.05g step (4)2It is anhydrous that-HETMS micro-capsule is dispersed in 20mL
In ethyl alcohol, the 3- aminopropyl triethoxysilane (APTES) of 120 μ L is added into system, after reacting 10h at 80 DEG C, by institute
The material ethanol washing obtained carries out vacuum drying and obtains the hydrophobic Janus grading-hole SiO of inner surface hydrophilic outer surface2Micro-capsule
(APTES-SiO2- HETMS) material；
Attached drawing 8 is to useModel DSA30 optical contact angle measuring instrument measures having an open structure amphipathic
Janus grading-hole APTES-SiO2The contact angle (149 °) of-HETMS micro-capsule, shows that hydrophobic chain is successfully modified to the appearance of micro-capsule
Face；
Attached drawing 9 is the amphiphilic having an open structure scanned with Japan Electronics model JEM-1011 transmission electron microscope
Property Janus grading-hole APTES-SiO2The TEM photo of the inner surface load gold particle of-HETMS micro-capsule, can be seen that from photo
Gold particle is mostly present in the inner surface of micro-capsule, shows that amino is successfully modified to the inner surface of micro-capsule；
The amphipathic Janus grading-hole micro-capsule having an open structure that the present invention obtains has high mechanical stability and good
Good organic solvent resistance, the experiment proved that, during high speed centrifugation (12000r/min) separation, supersound washing, micro-capsule
Complete pattern can still be maintained；And organic solvent is used in experimentation and removes removing template, organic solvent is to material sheet
Body does not influence；
Embodiment two:
(1) preparation of the 500nm dodecyl sodium sulfate as the linear polystyrene template microsphere of emulsifier
240mL water and 0.2g sodium bicarbonate, 0.075g SDS are added in the reactor, stirs 10min, under protection of argon gas
40mL styrene monomer is added in reaction system, 30min is emulsified, after system temperature is risen to 70 DEG C, by 0.32g persulfuric acid
Potassium (KPS) is dissolved in 60mL water, and potassium persulfate solution is added dropwise in reaction system with 30min, and mixing speed is controlled in 180r/
Min stops reaction after reacting 13h, by material centrifugal sedimentation, the monodispersed linear polyphenyl second of 500nm is obtained after vacuum drying
Alkene template microsphere；
(2)LPS@SiO2The preparation of core shell complex microsphere
(25 DEG C) are by 1g linear polystyrene template microsphere obtained in dry step (1) method two in 60mL at room temperature
10min is impregnated in the concentrated sulfuric acid (98Wt%), then reacts 1h at 40 DEG C of dislocation, material is washed till neutrality with water after reaction,
The polystyrene microsphere that sulfonic acid group functionalization is obtained after freeze-drying, by the polyphenyl of the 1g sulfonic acid group functionalization of these dryings
Ethylene microballoon is dispersed in 120mL dehydrated alcohol, 16mL TEOS, 16mL water is successively added into system, at room temperature (25 DEG C)
12h is reacted, washes two to obtaining LPS@SiO three times, after vacuum drying with ethyl alcohol after reaction2Core shell complex microsphere；
(3) the LPS@SiO of outer surface hydrophobically modified2The preparation of complex microsphere is the same as one step of embodiment (3)；
(4) grading-hole SiO having an open structure2The preparation of-HETMS micro-capsule
By the hydrophobic 0.2g LPS SiO in outer surface obtained in dry step (3)2- HETMS complex microsphere is dispersed in
In 4mL dehydrated alcohol, 8mL tetrahydrofuran (THF)/dehydrated alcohol (1:2v/v) mixed solution is injected into rapidly reaction system
In, (25 DEG C) swelling 1h, obtain anisotropic LPS@SiO at room temperature2Material, is then centrifuged out by-HETMS complex microsphere
To use pure THF centrifuge washing 3-5 times, then with ethyl alcohol THF is washed, can be prepared by after vacuum drying having an open structure outer
The grading-hole SiO of surface hydrophobicity2- HETMS micro-capsule；
(5) to SiO2- HETMS micro-capsule inner surface carries out hydrophilic modifying with one step of embodiment (5)；
Attached drawing 10 is to useThe amphiphilic having an open structure that model DSA30 optical contact angle measuring instrument measures
Property Janus grading-hole APTES-SiO2The contact angle (138 °) of-HETMS micro-capsule shows that hydrophobic chain is successfully modified to the outer of micro-capsule
Surface；
Attached drawing 11 is obtained with the surfaces externally and internally functionalization of 450 scanning of scanning electron microscope of model FEI Nano SEM
The amphipathic Janus grading-hole APTES-SiO having an open structure arrived2The electromicroscopic photograph of-HETMS micro-capsule；
Embodiment three:
(1) preparation of the linear polystyrene template microsphere of 800nm PVP functionalization is the same as one step of embodiment (1)；
(2)LPS@TiO2The preparation of core shell complex microsphere
The linear polystyrene template microsphere of 1gPVP functionalization obtained in dry step (1) method one is dispersed in
In 50mL dehydrated alcohol, by the mixed solution note of 50mL Butyl Phthalate (TBT)/dehydrated alcohol (v/v 1:1) to above-mentioned dispersion liquid
In, (25 DEG C) stirring 8h, unadsorbed TBT is washed away with dehydrated alcohol, material is then dispersed in the anhydrous second of 50mL at room temperature
In alcohol, 50mL water is added into system, at room temperature (25 DEG C) reaction 6h, washes two with ethyl alcohol after reaction and arrive three times, vacuum
LPS@TiO is obtained after drying2Core shell complex microsphere；
(3) the LPS@TiO of outer surface hydrophobically modified2The preparation of complex microsphere
By dry 0.1g LPS@TiO2Core shell complex microsphere is dispersed in dehydrated alcohol, and 60 μ L ten are added into system
After reacting 10h at 80 DEG C, by resulting material ethanol washing, it is dry to carry out vacuum for six alkyl trimethoxysilanes (HETMS)
It is dry to obtain the hydrophobic LPS@TiO in outer surface2Complex microsphere (LPS@TiO2-HETMS)；
(4) grading-hole TiO having an open structure2The preparation of-HETMS micro-capsule
By the hydrophobic 0.2g LPS TiO in outer surface obtained in dry step (3)2- HETMS complex microsphere is dispersed in
In 4mL dehydrated alcohol, 8mL tetrahydrofuran (THF)/dehydrated alcohol (1:4v/v) mixed solution is injected into rapidly reaction system
In, (25 DEG C) swelling 1h, obtain anisotropic LPS@TiO at room temperature2Material, is then centrifuged out by-HETMS complex microsphere
To use pure THF centrifuge washing 3-5 times, then with ethyl alcohol THF is washed, can be prepared by after vacuum drying having an open structure outer
The grading-hole TiO of surface hydrophobicity2- HETMS micro-capsule；
(5) to TiO2- HETMS micro-capsule inner surface carries out hydrophilic modifying
By the hydrophobic TiO in outer surface obtained in dry 0.05g step (4)2It is anhydrous that-HETMS micro-capsule is dispersed in 20mL
In ethyl alcohol, the 3- aminopropyl triethoxysilane (APTES) of 120 μ L is added into system, after reacting 10h at 80 DEG C, by institute
The material ethanol washing obtained carries out vacuum drying and obtains the hydrophobic Janus grading-hole TiO of inner surface hydrophilic outer surface2Micro-capsule
(APTES-TiO2- HETMS) material；
Example IV:
(1) 500nm dodecyl sodium sulfate makees the preparation of the linear polystyrene template microsphere of emulsifier with embodiment two
Step (1)；
(2)LPS@TiO2The preparation of core shell complex microsphere
(25 DEG C) are by 1g linear polystyrene template microsphere obtained in dry step (1) method two in 60mL at room temperature
10min is impregnated in the concentrated sulfuric acid (98Wt%), then reacts 1h at 40 DEG C of dislocation, material is washed till neutrality with water after reaction,
The polystyrene microsphere that sulfonic acid group functionalization is obtained after freeze-drying, by the linear of the 1g sulfonic acid group functionalization of these dryings
Polystyrene microsphere is dispersed in 50mL dehydrated alcohol, by the mixing of 50mL Butyl Phthalate (TBT)/dehydrated alcohol (v/v 1:1)
Solution is infused into above-mentioned dispersion liquid, and (25 DEG C) stirring 8h, unadsorbed TBT are washed away with dehydrated alcohol, then by material at room temperature
Material is dispersed in 50mL dehydrated alcohol, and 50mL water is added into system, reacts 6h under mechanical stirring, uses ethyl alcohol after reaction
Two are washed to obtaining LPS@TiO three times, after vacuum drying2Core shell complex microsphere；
(3) the LPS@TiO of outer surface hydrophobically modified2The preparation of complex microsphere is the same as three step of embodiment (3)；
(4) grading-hole TiO having an open structure2The preparation of-HETMS micro-capsule is the same as three step of embodiment (4)；
(5) to TiO2- HETMS micro-capsule inner surface carries out hydrophilic modifying with three step of embodiment (5)；
Embodiment five:
(1) preparation of the linear polystyrene template microsphere of 800nm PVP functionalization is the same as one step of embodiment (1)；
(2)LPS@SiO2The preparation of core shell complex microsphere is the same as one step of embodiment (2)；
(3) the modified LPS@SiO of surface and hydrophilic outer2The preparation of complex microsphere
By dry 0.1g LPS@SiO2Core shell complex microsphere is dispersed in dehydrated alcohol, and 60mL is added into system
3- aminopropyl triethoxysilane (APTES) after reacting 10h at 80 DEG C, by resulting material ethanol washing, carries out vacuum
It is dry to obtain LPS@SiO2- APTES complex microsphere；
(4) grading-hole SiO having an open structure2The preparation of-APTES micro-capsule is the same as one step of embodiment (4)；
(5) to SiO2- APTES micro-capsule inner surface carries out hydrophobically modified；
By the SiO of surface and hydrophilic outer obtained in dry 0.05g step (4)2It is anhydrous that-APTES micro-capsule is dispersed in 20mL
In ethyl alcohol, the hexadecyl trimethoxy silane (HETMS) of 120 μ L is added into system, after reacting 10h at 80 DEG C, by institute
The material ethanol washing obtained carries out the Janus grading-hole SiO that vacuum drying obtains hydrophobic inner surface and hydrophilic outer surface2Micro-capsule
(HETMS-SiO2- APTES) material；
Embodiment five:
(1) preparation of the linear polystyrene template microsphere of 800nm PVP functionalization is the same as one step of embodiment (1)；
(2)LPS@SiO2The preparation of core shell complex microsphere is the same as one step of embodiment (2)；
(3) the modified LPS@SiO of surface and hydrophilic outer2The preparation of complex microsphere
By dry 0.1g LPS@SiO2Core shell complex microsphere is dispersed in dehydrated alcohol, and 60mL is added into system
3- mercaptopropyl trimethoxysilane after reacting 10h at 80 DEG C, by resulting material ethanol washing, carries out vacuum drying and obtains
Obtain the LPS@SiO of surface and hydrophilic outer2- SH complex microsphere；
(4) grading-hole SiO having an open structure2The preparation of-SH micro-capsule is the same as one step of embodiment (4)；
(5) to SiO2- SH micro-capsule inner surface carries out hydrophobically modified；
By the SiO of surface and hydrophilic outer obtained in dry 0.05g step (4)2- SH micro-capsule is dispersed in 20mL dehydrated alcohol
In, triethoxy (nine fluorine hexyl of 1H, 1H, 2H, 2H-) silane of 120 μ L is added into system, it, will after reacting 10h at 80 DEG C
Resulting material ethanol washing carries out the Janus grading-hole SiO that vacuum drying obtains hydrophobic inner surface and hydrophilic outer surface2It is micro-
Capsule material；
Embodiment six:
(1) preparation of the linear polystyrene template microsphere of 800nm PVP functionalization is the same as one step of embodiment (1)；
(2)LPS@SiO2The preparation of core shell complex microsphere is the same as one step of embodiment (2)；
(3) the modified LPS@SiO of surface and hydrophilic outer2The preparation of complex microsphere
By dry 0.1g LPS@SiO2Core shell complex microsphere is dispersed in dehydrated alcohol, and 60mL carboxylic is added into system
Three sodium alkoxide of base ethylsilane, by resulting material ethanol washing, it is dilute to be subsequently dispersed 10mL after reacting 10h at 80 DEG C
It is acidified 6h in hydrochloric acid (5Wt%), is washed with water to neutrality, carries out the LPS@SiO that vacuum drying obtains surface and hydrophilic outer2- COOH is multiple
Close microballoon；
(4) grading-hole SiO having an open structure2The preparation of-COOH micro-capsule is the same as one step of embodiment (4)；
(5) to SiO2- COOH micro-capsule inner surface carries out hydrophobically modified；
By the SiO of surface and hydrophilic outer obtained in dry 0.05g step (4)2- SH micro-capsule is dispersed in 20mL dehydrated alcohol
In, triethoxy (nine fluorine hexyl of 1H, 1H, 2H, 2H-) silane of 120 μ L is added into system, it, will after reacting 10h at 80 DEG C
Resulting material ethanol washing carries out the Janus grading-hole SiO that vacuum drying obtains hydrophobic inner surface and hydrophilic outer surface2It is micro-
Capsule material；
Unaccomplished matter of the present invention is well-known technique.
Claims (5)
1. a kind of preparation method of amphipathic Janus grading-hole micro-capsule having an open structure, it is characterized in that this method include with
Lower step:
1) average particle size range the linear polystyrene template microsphere of 80~1000nm preparation, be following two method it
One:
Method one: polyvinylpyrrolidone is used to prepare linear polystyrene moulding microballoon as emulsifier
Water and polyvinylpyrrolidone (PVP) are added in the reactor, 10min is stirred, under protection of argon gas by styrene monomer
It is added in reaction system, emulsifies 30min, after system temperature is risen to 70 DEG C, potassium peroxydisulfate (KPS) solution is added dropwise to reaction
In system, after reacting 10~15h under stiring, stops reaction, by material centrifugal sedimentation, obtain 80~1000nm after vacuum drying
The monodispersed linear polystyrene template microsphere of range；
It is water that its material proportion, which is volume ratio: styrene: KPS solution=90:10:10；0.01~9.0g is added in the water of 90mL
PVP；The concentration of KPS solution is in the water of 10mL dissolved with 0.01~0.8g potassium peroxydisulfate；
Alternatively, method two: dodecyl sodium sulfate being used to prepare linear polystyrene moulding microballoon as emulsifier
Water and sodium bicarbonate, dodecyl sodium sulfate (SDS) are added in the reactor, 10min is stirred, under protection of argon gas by benzene
Vinyl monomer is added in reaction system, emulsifies 30min, and after system temperature is risen to 70 DEG C, potassium peroxydisulfate (KPS) solution is dripped
It adds in reaction system, after reacting 10~15h under stiring, stops reaction, by material centrifugal sedimentation, obtain 80 after vacuum drying
The monodispersed linear polystyrene template microsphere of~1000nm range；
It is water that its material proportion, which is volume ratio: styrene: KPS solution=12:2:3；It is added 0.025~2g's in the water of 240mL
The sodium bicarbonate of SDS and 0.05~0.4g；The concentration of KPS solution is in the water of 60mL dissolved with 0.1~0.9g potassium peroxydisulfate；
2) preparation of core shell complex microsphere is one of following four method:
One: PVP method of method prepares linear polystyrene SiO2Core shell complex microsphere
The linear polystyrene template microsphere of PVP functionalization obtained in dry step 1) method one is dispersed in dehydrated alcohol
In, ammonium hydroxide and water are successively added into system, after stirring 5~20min, ethyl orthosilicate (TEOS) is added into system, in room
After 6~10h of the lower reaction of temperature, by resulting material ethanol washing, carries out vacuum drying and obtain linear polystyrene@SiO2Core/
Shell composite microsphere material；
It is dehydrated alcohol that its material proportion, which is volume ratio: ammonium hydroxide: water: TEOS=120:0.1~1.2:1~16:1~16；Often
0.1g linear polystyrene template microsphere is dispersed in the dehydrated alcohol of 5~20mL；
Alternatively, method two: sulfonation method prepares linear polystyrene SiO2Core shell complex microsphere
Linear polystyrene template microsphere obtained in dry step 1) method two is impregnated 10 in concentrated sulfuric acid at room temperature~
Then 30min reacts 0.25~8h at 40 DEG C of dislocation, material is washed till neutrality with water after reaction, is obtained after freeze-drying
The polystyrene microsphere of sulfonic acid group functionalization；
The polystyrene microsphere of dry sulfonic acid group functionalization is dispersed in dehydrated alcohol, is successively added into system
TEOS, water, react 10 at room temperature~for 24 hours, two are washed to obtaining linear polyphenyl three times, after vacuum drying with ethyl alcohol after reaction
Ethylene@SiO2Core shell complex microsphere；
Its material proportion is that the amount of the corresponding concentrated sulfuric acid of every sulfonation 1g linear polystyrene template microsphere is 20~80mL；Every 1g sulphur
The polystyrene microsphere of acid groups functionalization is dispersed in the dehydrated alcohol of 50~200mL；Volume ratio is dehydrated alcohol: TEOS:
Water=10:0.2~2:0.2~2；
Alternatively, three: PVP method of method prepares linear polystyrene TiO2Core shell complex microsphere
The linear polystyrene template microsphere of PVP functionalization obtained in dry step 1) method one is dispersed in dehydrated alcohol
In, by Butyl Phthalate/dehydrated alcohol mixed solution note into above-mentioned dispersion liquid, 6~12h is stirred at room temperature, with anhydrous second
Alcohol washes away unadsorbed Butyl Phthalate, and then obtained material is dispersed in dehydrated alcohol, water is added into system, in room temperature
6~12h of lower reaction is arrived with ethanol washing two obtain linear polystyrene@TiO three times, after vacuum drying after reaction2Core/
Shell complex microsphere；
Its material proportion is that the linear polystyrene template microsphere of every 1g PVP functionalization is dispersed in the dehydrated alcohol of 25~100mL
In, and into dispersion liquid inject 20~80mL Butyl Phthalate/dehydrated alcohol mixed solution；In mixed solution, volume ratio
Dehydrated alcohol: Butyl Phthalate=1:0.5~2；Every 1g washes away the material after unadsorbed Butyl Phthalate and is dispersed in 25~100mL's
In dehydrated alcohol, volume ratio is dehydrated alcohol needed for dispersion washes away the material after unadsorbed Butyl Phthalate: water=1:0.5~
2；
Alternatively, method four: sulfonation method prepares linear polystyrene TiO2Core shell complex microsphere
Linear polystyrene template microsphere obtained in dry step 1) method two is impregnated 10 in concentrated sulfuric acid at room temperature~
Then 30min reacts 0.25~8h at 40 DEG C of dislocation, material is washed till neutrality with water after reaction, is obtained after freeze-drying
The polystyrene microsphere of sulfonic acid group functionalization；
The polystyrene microsphere of sulfonic acid group functionalization of these dryings is dispersed in dehydrated alcohol, by Butyl Phthalate/anhydrous
The mixed solution of ethyl alcohol is infused into above-mentioned dispersion liquid, and 6~12h is stirred at room temperature, unadsorbed phthalandione is washed away with dehydrated alcohol
Then obtained material is dispersed in dehydrated alcohol by butyl ester, water is added into system, reacts 6~12h, reaction at room temperature
After with ethyl alcohol wash two to obtaining linear polystyrene@TiO three times, after vacuum drying2Core shell complex microsphere；
Its material proportion is that the amount of the corresponding concentrated sulfuric acid of every sulfonation 1g linear polystyrene template microsphere is 20~80mL；Every 1g sulphur
The polystyrene microsphere of acid groups functionalization is dispersed in the dehydrated alcohol of 25~100mL, and into dispersion liquid injection 20~
Butyl Phthalate/dehydrated alcohol mixed solution of 80mL；In mixed solution, volume ratio is dehydrated alcohol: Butyl Phthalate=1:0.5
~2；Every 1g washes away the material after unadsorbed Butyl Phthalate and is dispersed in the dehydrated alcohol of 25~100mL；Volume ratio is dispersion
Dehydrated alcohol needed for washing away after the microballoon of unadsorbed Butyl Phthalate: water=1:0.5~2；
3) preparation of hydrophobic, the hydrophilic core shell complex microsphere in outer surface
Method one: the preparation of the hydrophobic core shell complex microsphere in outer surface
Any one in four kinds of core shell complex microspheres obtained in dry step 2) is dispersed in dehydrated alcohol, Xiang Ti
The silane coupling agent being added in system, by resulting material ethanol washing, is dried in vacuo after reacting 5~12h at 80 DEG C
Obtain the hydrophobic core shell complex microsphere in outer surface；
Its material proportion is that every 0.1g core shell complex microsphere is dispersed in the dehydrated alcohol of 5~20mL, and 20~120 μ are added
L silane coupling agent；Silane coupling agent is the silane coupling agent with hydrophobic chain；
Method two: the preparation of the core shell complex microsphere of surface and hydrophilic outer
Any one in four kinds of core shell complex microspheres obtained in dry step 2) is dispersed in dehydrated alcohol, Xiang Ti
Silane coupling agent is added in system, after reacting 5~12h at 80 DEG C, by resulting material ethanol washing, carries out vacuum drying and obtains
Obtain the core shell complex microsphere of surface and hydrophilic outer；
Its material proportion are as follows: every 0.1g core shell complex microsphere is dispersed in the dehydrated alcohol of 5~20mL, and is added 20~120
μ L silane coupling agent；Silane coupling agent be end with amino, carboxyl, sulfydryl silane coupling agent；
4) preparation of grading-hole micro-capsule having an open structure
The core shell of the hydrophobic core shell complex microsphere in outer surface obtained in dry step 3) or surface and hydrophilic outer is compound
Microballoon is dispersed in dehydrated alcohol, and tetrahydrofuran (THF)/dehydrated alcohol mixed solution is injected into reaction system rapidly,
It is swollen 0.2~2h at room temperature, obtains anisotropic complex microsphere, then material is centrifuged out and is washed with pure THF centrifugation
It washs 3~5 times, then washes THF with ethyl alcohol, can be prepared by that outer surface having an open structure is hydrophobic or appearance after vacuum drying
The hydrophilic grading-hole micro-capsule in face；
The core shell complex microsphere of the hydrophobic core shell complex microsphere in every outer surface 0.2g or surface and hydrophilic outer is dispersed in 1~8mL
Dehydrated alcohol in, and into dispersion liquid inject 2~16mL THF/ dehydrated alcohol mixed solution；In mixed solution, body
Product is than being THF: dehydrated alcohol=1~6:6；
5) micro-capsule inner surface carries out hydrophobic, hydrophile function
Method one: the preparation of the hydrophobic Janus grading-hole micro-capsule of inner surface hydrophilic outer surface
The hydrophobic grading-hole micro-capsule in obtained outer surface having an open structure is dispersed in dehydrated alcohol, is added into system
Silane coupling agent after reacting 5~12h at 80 DEG C, by resulting material ethanol washing, carries out vacuum drying and obtains inner surface
The hydrophobic Janus grading-hole microencapsulated material of hydrophilic outer surface；
Its material proportion are as follows: every 0.05g grading-hole micro-capsule is dispersed in 5~40mL dehydrated alcohol, and 20~240 μ L silicon are added
Alkane coupling agent；Silane coupling agent be end with amido, carboxyl, sulfydryl silane coupling agent；
Method two: the preparation of the Janus grading-hole micro-capsule of hydrophobic inner surface and hydrophilic outer surface
The grading-hole micro-capsule of obtained surface and hydrophilic outer having an open structure is dispersed in dehydrated alcohol, is added into system
Silane coupling agent after reacting 5~12h at 80 DEG C, by resulting material ethanol washing, carries out vacuum drying and obtains inner surface
The hydrophilic Janus grading-hole microencapsulated material of hydrophobic external surface；
Its material proportion are as follows: every 0.05g grading-hole micro-capsule is dispersed in 5~40mL dehydrated alcohol, and 20~240 μ L silicon are added
Alkane coupling agent；Silane coupling agent is the silane coupling agent with hydrophobic chain.
2. the preparation method of amphipathic Janus grading-hole micro-capsule having an open structure as described in claim 1, it is characterized in that
Silane coupling agent of the end with carboxyl is specially three sodium alkoxide of carboxyethylsilane.
3. the preparation method of amphipathic Janus grading-hole micro-capsule having an open structure as described in claim 1, it is characterized in that
Silane coupling agent of the end with sulfydryl is 3- mercaptopropyl trimethoxysilane, 3- mercaptopropyltriethoxysilane or 11-
Mercapto-undecanoic base trimethoxy silane.
4. the preparation method of amphipathic Janus grading-hole micro-capsule having an open structure as described in claim 1, it is characterized in that
Silane coupling agent of the end with amido is 3- aminopropyl triethoxysilane, 3- aminopropyl trimethoxysilane, 4- ammonia
Base butyl triethoxysilane, N- (2- amino-ethyl)-aminopropyl triethoxysilane, N- (2- amino-ethyl)-aminopropyl three
Methoxy silane, N- (6- Aminohexyl) amino methyl triethoxysilane, N- [3- trimethoxy first silicon substrate] propyl] -1,6-
Hexamethylene diamine, 11- amino-undecanoic ethyl triethoxy silicane alkane, 3- (4- Semicarbazido) propyl-triethoxysilicane or diethylenetriamine base
Propyl trimethoxy silicane.
5. the preparation method of amphipathic Janus grading-hole micro-capsule having an open structure as described in claim 1, it is characterized in that
Silane coupling agent of the end with hydrophobic chain is octadecyl trimethoxysilane, octadecyltriethoxy silane, ten
Six alkyl trimethoxysilanes, hexadecyl, dodecyltrimethoxysilane, dodecyl triethoxy
Silane, eight alkyl trimethoxysilanes, eight alkyl triethoxysilanes, n-hexyl trimethoxy silane, n-hexyl triethoxy
Silane, trimethoxy-(2,4,4- tri-methyl-amyl) silane, triethoxy-(2,4,4- tri-methyl-amyl) silane, vinyl three
Ethoxysilane, 5- hexenyl triethoxysilane, 7- octenyl trimethoxy silane, 10- alkenyl undecyl trimethoxy
Silane,
1H, 1H, 2H, 2H- perfluoro capryl triethoxysilane, 1H, 1H, 2H, 2H- perfluoro capryl trimethoxy silane, trimethoxy
Base (nine fluorine hexyl of 1H, 1H, 2H, 2H-) silane or triethoxy (nine fluorine hexyl of 1H, 1H, 2H, 2H-) silane.
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| CN101513607A (en) * | 2009-02-19 | 2009-08-26 | 浙江大学 | Method for preparation of composite chromatographic stuffing of polymer carbon nanometer tube |
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| CN101513607A (en) * | 2009-02-19 | 2009-08-26 | 浙江大学 | Method for preparation of composite chromatographic stuffing of polymer carbon nanometer tube |
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